EP3174708B1 - Furan based polyamides and articles made therefrom - Google Patents
Furan based polyamides and articles made therefrom Download PDFInfo
- Publication number
- EP3174708B1 EP3174708B1 EP15760318.4A EP15760318A EP3174708B1 EP 3174708 B1 EP3174708 B1 EP 3174708B1 EP 15760318 A EP15760318 A EP 15760318A EP 3174708 B1 EP3174708 B1 EP 3174708B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- furan
- diamine
- group
- acid
- multilayer structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims description 203
- 229920002647 polyamide Polymers 0.000 title claims description 145
- 239000004952 Polyamide Substances 0.000 title claims description 143
- 230000004888 barrier function Effects 0.000 claims description 93
- 239000007789 gas Substances 0.000 claims description 82
- -1 aliphatic diamine Chemical class 0.000 claims description 75
- 150000004985 diamines Chemical class 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 64
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 52
- 229920000642 polymer Polymers 0.000 claims description 48
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 38
- 229920002959 polymer blend Polymers 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 28
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 150000004984 aromatic diamines Chemical class 0.000 claims description 16
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 13
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 13
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 13
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 229920002313 fluoropolymer Polymers 0.000 claims description 9
- 239000004811 fluoropolymer Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000000123 paper Substances 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000014171 carbonated beverage Nutrition 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 118
- 239000000047 product Substances 0.000 description 42
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 29
- 229920002292 Nylon 6 Polymers 0.000 description 26
- 229920001577 copolymer Polymers 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 230000035699 permeability Effects 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 10
- 229920001038 ethylene copolymer Polymers 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000000113 differential scanning calorimetry Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- 229920000572 Nylon 6/12 Polymers 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 5
- 229920003235 aromatic polyamide Polymers 0.000 description 5
- 150000002118 epoxides Chemical group 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000000196 viscometry Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 229920000577 Nylon 6/66 Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229940123973 Oxygen scavenger Drugs 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229920003231 aliphatic polyamide Polymers 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 3
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 229940117958 vinyl acetate Drugs 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GDYYIJNDPMFMTB-UHFFFAOYSA-N 2-[3-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC(CC(O)=O)=C1 GDYYIJNDPMFMTB-UHFFFAOYSA-N 0.000 description 2
- XHALKWMTKWHQLO-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 XHALKWMTKWHQLO-UHFFFAOYSA-N 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- FWEOQOXTVHGIFQ-UHFFFAOYSA-N 8-anilinonaphthalene-1-sulfonic acid Chemical compound C=12C(S(=O)(=O)O)=CC=CC2=CC=CC=1NC1=CC=CC=C1 FWEOQOXTVHGIFQ-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- This disclosure relates to multilayer structures comprising polymeric gas permeation barrier layers comprising a furan-based polyamide and articles made therefrom and methods of improving the shelf life of products.
- Gas barrier properties are one of the key requirements for polymers used in packaging applications to protect the contents and provide desired shelf-life.
- the prevention of oxygen permeation for example inhibits oxidation and microbial growth, whereas prevention of water vapor permeation retains liquid content or protects the contents against water degradation (mold).
- PET poly(ethylene terephthalate)
- PE polyethylene
- PVOH poly(vinyl alcohol)
- EvOH poly(ethylene vinyl alcohol)
- PAN poly(ethylene naphthalene)
- PEN poly(ethylene naphthalene)
- MXD6 poly(vinylidene chloride)
- PVdC poly(vinylidene chloride)
- EvOH exhibits good oxygen barrier at low humidity levels but fails at room temperature and high levels of humidity or under retort conditions (retort shock).
- PET has relatively high tensile strength but is limited by modest water and oxygen barrier properties.
- PVOH cannot be extruded as it is thermally unstable below its melting point.
- PVDC while being an excellent gas/water barrier resin has environmental limitations.
- Aliphatic polyamides e.g. PA 6 or 6,66
- PA 6 or 6,66 have moderate gas barrier performance and like PET have poor water barrier.
- EP 0411791 discloses gas barriers comprising at least one layer of an amorphous polyamide derivable from a nylon salt formed from aromatic dicarboxylic acids and diamines characterised in that a) the aromatic dicarboxylic acids comprise isophthalic acid and at least one other aromatic dicarboxylic acid selected from terephthalic acid, 4,4'-dicarboxy biphenyl and 2,6-naphthalene dicarboxylic acid, and b) the diamine comprises meta-xylylene diamine, the polyamide being a barrier against oxygen and/or carbon dioxide.
- WO 2014/012240 discloses a polyamide of the following formula: in which R represents a covalent bond or a divalent hydrocarbon-based group chosen from saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics and alkylaromatics.
- a multilayer structure comprising:
- the first layer is selected from the group consisting of polyurethane, polyester, polyolefin, polyamide, polyimide, polycarbonate, polyether, polyacrylates, styrenics, fluoropolymer, polyvinylchlorides, epoxies, EVOH and polysiloxanes.
- the furan-based polyamide comprises the following repeat unit: wherein R is selected from the group consisting of an aliphatic, an aromatic and an alkylaromatic group.
- R is a C2-C18 hydrocarbon or fluorocarbon group.
- the one or more diamines of the furan-based polyamide includes an aliphatic diamine comonomer selected from 1,2-ethylenediamine; trimethylenediamine; 1,4-tetramethylenediamine; 1,5-pentamethylenediamine; 2-methyl pentamethylenediamine; and 1,6-hexamethylenediamine.
- the gas permeation barrier layer is a polymer blend of the furan-based polyamide and a polymer selected from the group consisting of polyurethanes, polyesters, polyolefins, polyamides, polyimides, polycarbonates, polyethers, polyacrylates, styrenics, fluoropolymers, polysiloxanes, EVOH, and mixtures thereof, wherein the furan-based polyamide is present in an amount in the range of 0.1 -99.9% by weight, based on the total weight of the polymer blend.
- the gas permeation barrier layer is a polymer blend comprising poly(trimethylene furandicarbonamide) (3AF) and a second furan-based polyamide different from 3AF, and wherein the amount of 3AF is 0.1-99.9% by weight, based on the total weight of the polymer blend.
- the multilayer structure further comprises a second layer disposed on at least a portion of the gas permeation barrier layer, such that at least a portion of the gas permeation barrier layer is sandwiched between the first tie layer and the second layer.
- the furan-based polyamide is a furan-based polyamide is derived from:
- the multilayer structure there is an article comprising the multilayer structure, wherein the article is a film, a sheet, a coating, shaped or modeled article, a layer in a multilayer laminate, filaments, fibers, spun yarn, woven fabric, garment, or non-woven web, and wherein the multilayer structure provides gas permeation barrier to a product.
- the product is at least one of an oxygen-sensitive product, a moisture-sensitive product, or a carbonated beverage.
- one or more of A, B, and C implies any one of the following: A alone, B alone, C alone, a combination of A and B, a combination of B and C, a combination of A and C, or a combination of A, B, and C.
- biologically-derived as used herein is used interchangeably with “biobased” or “bio-derived” and refers to chemical compounds including monomers and polymers, that are obtained in whole or in any part, from any renewable resources including but not limited to plant, animal, marine materials or forestry materials.
- biobased content of any such compound shall be understood as the percentage of a compound's carbon content determined to have been obtained or derived from such renewable resources.
- furandicarboxylic acid as used herein is used interchangeably with furandicarboxylic acid; 2,5-furandicarboxylic acid; 2,4-furandicarboxylic acid; 3,4-furandicarboxylic acid; and 2,3-furandicarboxylic acid.
- FDCA 2,5-furandicarboxylic acid
- dehydromucic acid is also known as dehydromucic acid, and is an oxidized furan derivative, as shown below:
- dicarboxylic acid as used herein is used interchangeably with “diacid”.
- furan 2,5-dicarboxylic acid (FDCA) or a derivative thereof as used herein is used interchangeably with “furan 2,5-dicarboxylic acid (FDCA) or a functional equivalent thereof” and refers to any suitable isomer of furandicarboxylic acid or derivative thereof such as, 2,5-furandicarboxylic acid; 2,4-furandicarboxylic acid; 3,4-furandicarboxylic acid; 2,3-furandicarboxylic acid or their derivatives.
- the hydrogens at the 3 and/or 4 position on the furan ring can, if desired, be replaced, independently of each other, with -CH 3 , -C 2 H 5 , or a C 3 to C 25 straight-chain, branched or cyclic alkane group, optionally containing one to three heteroatoms selected from the group consisting of O, N, Si and S, and also optionally substituted with at least one member selected from the group consisting of -Cl, -Br, -F, -I, -OH, -NH 2 and -SH.
- a derivative of 2,5-furan dicarboxylic acid can also be prepared by substitution of an ester or halide at the location of one or both of the acid moieties.
- carrier as used herein is used interchangeably with “permeation rate” or “permeability rate” or “transmission rate” to describe the gas barrier properties, with low permeation rate or low transmission rate in a material implying that the material has a high barrier.
- carrier and “barrier layer”, as applied to multilayer structures, refer to the ability of a structure or layer to serve as a barrier to a fluid permeation (e.g. a gas or a liquid).
- a fluid permeation e.g. a gas or a liquid
- oxygen barrier properties are measured according to ASTM D3985-05; carbon dioxide barrier properties are measured according to ASTM F2476-05; and moisture barrier properties are measured according to ASTM F1249-06.
- furan-based polyamide refers to any furan-based homo-polyamide or furan-based co-polyamide comprising at least one monomeric unit derived from furan dicarboxylic acid (FDCA) or a derivative thereof, such as FDME, FDC-Cl or the like.
- FDCA furan dicarboxylic acid
- FDC-Cl FDC-Cl
- the gas permeation barrier layer may comprise a polymer blend composition comprising a polymer blend of a furan-based polyamide and a polymer selected from the group consisting of polyurethanes, polyesters, polyolefins, polyamides, polyimides, polycarbonates, polyethers, polyacrylates, styrenics, fluoropolymers, polysiloxanes, EVOH, and mixtures thereof.
- the furan-based polyamide is derived from:
- the furan-based polyamide is present in an amount in the range of 0.1-99.9% or 0.5-80% or 1-50% by weight, based on the total weight of the polymer blend.
- the furan-based polyamide can be derived from any suitable dicarboxylic acid such as a linear aliphatic diacid, a cycloaliphatic diacid, an aromatic diacid, an alkylaromatic diacid or mixtures thereof.
- the aliphatic diacid may include from 2 to 18 carbon atoms in the main chain.
- Suitable aliphatic diacids include, but are not limited to, oxalic acid; fumaric acid; maleic acid; succinic acid; glutaric acid; adipic acid; pimelic acid; suberic acid; azelaic acid; sebacic acid; itaconic acid; malonic acid; mesaconic acid; dodecanediacid; undecanedioic acid; 1,12-dodecanedioic acid; 1,14-tetradecanedioic acid; 1,16-hexadecanedioic acid; 1,18-octadecanedioic acid; diabolic acid; and mixtures thereof.
- Suitable cycloaliphatic diacids include, but are not limited to, hexahydrophthalic acids, cis- and trans-1,4-cyclohexanedicarboxylic acid, cis- and trans-1,3-cyclohexanedicarboxylic acid, cis- and trans-1,2-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, trans-1,2,3,6-tetrahydrophthalic acid, hexahydrophthalic anhydride, and dihydrodicyclopentadienedicarboxylic acid.
- An aromatic diacid may include a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple condensed rings in which at least one is aromatic, (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl), which is optionally mono-, di-, or trisubstituted with, e.g., halogen, lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl, lower acyloxy, aryl , heteroaryl, and hydroxy.
- a single ring e.g., phenyl
- multiple rings e.g., biphenyl
- Suitable aromatic diacids include, but are not limited to, phthalic acid; isophthalic acid; p-(t-butyl)isophthalic acid; 1,2- or 1,3-phenylenediacetic acid; terephthalic acid; 2,5-dihydroxyterephthalic acid (DHTA); 4,4'-benzo-phenonedicarboxylic acid; 2,5 and 2,7-naphthalenedicarboxylic acid and mixtures thereof.
- Suitable alkylaromatic diacids include, but are not limited to, 1,2- or 1,3-phenylenediacetic acids, trimellitylimidoglycine, and 1,3-bis(4-carboxyphenoxy)propane.
- Examples of various hydroxy acids that can be included, in addition to the furan dicarboxylic acids, in the polymerization monomer makeup from which a copolymer can be made include glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxyvaleric acid, 7-hydroxyheptanoic acid, 8-hydroxycaproic acid, 9-hydroxynonanoic acid, or lactic acid; or those derived from pivalolactone, ⁇ -caprolactone or L,L, D,D or D,L lactides.
- esters of dicarboxylic acids described supra include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl or tert-butyl esters, more preferably the methyl, ethyl or n-butyl esters.
- diacids and their esters are obtained from renewable sources, such as azelaic acid, sebacic acid, succinic acid, and mixtures thereof.
- the furan-based polyamide is bio-derived or substantially bio-derived with the total content of bio-derived diacid in the range of 10-95% or 15-80% or 20-60% or 25-50% by moles with respect to the total molar content of the diacids and their esters in the polyamide.
- Suitable aliphatic diacid halides include, but are not limited to butylene diacid chloride; butylene diacid bromide; hexamethylene diacid chloride; hexamethylene diacid bromide; octamethylene diacid chloride; octamethylene diacid bromide; decamethylene diacid chloride; decamethylene diacid bromide; dodecamethylene diacid chloride; dodecamethylene diacid bromide; and mixtures thereof.
- Suitable aromatic diacid halide include, but are not limited to terephthaloyl dichloride; 4,4'-benzoyl dichloride; 2,6-naphthalenedicarboxyl acid dichloride; 1,5-naphthalene dicarboxyl acid dichloride; tolyl diacid chloride; tolylmethylene diacid bromide; isophorone diacid chloride; isophorone diacid bromide; 4,4'-methylenebis(phenyl acid chloride); 4,4'-methylenebis(phenyl acid bromide); 4,4'-methylenebis(cyclohexyl acid chloride); 4,4'-methylenebis(cyclohexyl acid bromide) and mixtures thereof.
- the furan-based polyamide can be derived from any suitable diamine comonomer (H 2 N-R-NH 2 ), where R (R 1 or R 2 ) is a linear aliphatic, a cycloaliphatic, aromatic or an alkylaromatic group.
- Suitable aliphatic diamine comonomer such as those with 2 to 12 number of carbon atoms in the main chain can be used.
- Suitable aliphatic diamines include, but are not limited to, 1,2-ethylenediamine; 1,6-hexamethylenediamine; 1,5-pentamethylenediamine; 1,4-tetramethylenediamine; 1,12-dodecanediamine; trimethylenediamine; 2-methyl pentamethylenediamine; heptamethylenediamine; 2-methyl hexamethylenediamine; 3-methyl hexamethylenediamine; 2,2-dimethyl pentamethylenediamine; octamethylenediamine; 2,5-dimethyl hexamethylenediamine; nonamethylenediamine; 2,2,4- and 2,4,4-trimethyl hexamethylenediamines; decamethylenediamine; 5-methylnonanediamine; undecamethylenediamine; dodecamethylenediamine; 2,
- Suitable cycloaliphatic diamines include, but are not limited to, bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; mixtures of 1,3- and 1,4-bis(aminomethyl)cyclohexane, 5-amino-1,3,3-trimethyl cyclohexanemethanamine; bis(p-aminocyclohexyl) methane, bis(aminomethyl)norbornane, 1,2-diaminocyclohexane, 1,4- or 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4- or 1,3-diaminocyclohexane, , isomeric mixtures of bis(4-aminocyclohexyl)methane, and mixtures thereof.
- Any suitable aromatic diamine comonomer such as those with ring sizes between 6 and 10 can be used.
- Suitable aromatic diamines include, but are not limited to para -phenylenediamine; 3,3'-dimethylbenzidine; 2,6-naphthylenediamine; 1,5-diaminonaphthalene, 4,4'-diaminodiphenyl ether; 4,4'-diaminodiphenyl sulfone; sulfonic- para- phenylene-diamine, 2,6-diamonopyridine, naphthidine diamine, benzidine, o-tolidine, and mixtures thereof.
- Suitable alkylaromatic diamines include, but are not limited to, 1,3-bis(aminomethyl)benzene, meta -xylylene diamine, para -xylylene diamine, 2,5-bis-aminoethyl- para -xylene, 9,9-bis(3-aminopropyl)fluorine, and mixtures thereof.
- At least one of the diamines is trimethylenediamine. In another embodiment, at least one of the diamine is tetramethylenediamine. In yet another embodiment, at least one of the diamine is decamethylenediamine.
- the furan-based polyamide is derived from a salt comprising diamine and a dicarboxylic acid, wherein the molar ratio of diamine and the dicarboxylic acid is 1:1. It is well known in the art that 1:1 diamine:diacid salts provide a means to control stoichiometry and to provide high molecular weight in step growth polymerizations such as that used to prepare polyamides.
- the number average molecular weight of the furan-based polyamide is at least 5000 g/mol, or at least 10000 g/mol, or at least 20000 g/mol or higher.
- the weight average molecular weight of the furan-based polyamide is at least 4 Kg/mol, or at least 40 Kg/mol, or at least 100 Kg/mol, or at least 150 Kg/mol, at least 200 Kg/mol.
- R R 1 , R 2 and R 3 .
- the repeat unit (1) is present in the range of 50.1-99.9 mol% or 55-98.5 mol% or 70-98.5 mol% or 85-98.5 mol% and the repeat unit (2) is present in the range of 0.1-49.9 mol% or 1.5-45 mol% or 1.50-30 mol% or 1.5-15 mol%, based on the total amount of furan-based polyamide composition.
- the furan-based polyamides as disclosed hereinabove, comprising the repeat units (1) and (2), as shown above, are statistical copolyamides where the repeat unit (1) may be adjacent to itself or adjacent to the repeat unit (2) and similarly the repeat unit (2) may be adjacent to itself or adjacent to the repeat unit (1).
- the total degree of polymerization of the furan-based polyamides comprising the repeat units (1) and (2) is in the range of 20-2000 or 20-1000 or 20-450.
- the furan-based polyamide is derived from:
- the furan-based polyamide is derived from furan dicarboxylic acid, terephthalic acid and one or more diamines, and comprises the following repeat units (1) and (3): wherein R 1 and R 2 are independently selected from the group consisting of an aliphatic, an aromatic and an alkylaromatic group.
- R 1 and R 2 are same. In another embodiment, R 1 and R 2 are different.
- the repeat unit (1) is present in the range of 50.1-99.9 mol% or 55-98.5 mol% or 70-98.5 mol% or 85-98.5 mol% and the repeat unit (3) is present in the range of 0.1-49.9 mol% or 1.5-45 mol% or 1.50-30 mol% or 1.5-15 mol%, based on the total amount of furan-based polyamide composition.
- the furan-based polyamides derived from furan dicarboxylic acid and terephthalic acid as disclosed hereinabove, comprising the repeat units (1) and (3), as shown above, are statistical copolyamides where the repeat unit (1) may be adjacent to itself or adjacent to the repeat unit (3) and similarly the repeat unit (3) may be adjacent to itself or adjacent to the repeat unit (1).
- the total degree of polymerization of the furan-based polyamides comprising the repeat units (1) and (3) is in the range of 20-2000 or 20-1000 or 20-450.
- the one or more diamines comprises at least one of 1,3 propane diamine and hexamethylene diamine.
- the furan-based polyamide is derived from furan dicarboxylic acid, terephthalic acid, 1,3 propane diamine and hexamethylene diamine.
- the polymer blend composition comprises a furan-based polyamide derived from:
- Any suitable diacid and diamines as disclosed hereinabove may be used.
- the furan-based polyamide is derived from:
- the first diamine is 1,3 propane diamine and the second diamine is hexamethylene diamine.
- the polymer blend composition comprises a furan-based polyamide derived from:
- Any suitable multifunctional acid may be used, including but not limited to, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, trimesic acid, and mixtures thereof.
- the polymer blend composition comprises a furan-based polyamide derived from:
- Any suitable multifunctional diamine may be used, including but not limited to, bis(hexamethylene)triamine, melamine, sym-triaminobenzene, triethylenetetramine, and mixtures thereof.
- the polymer blend composition comprises a polymer blend comprising a furan-based polyamide, as disclosed hereinabove, and a second polyamide.
- the second polyamide comprises an aliphatic polyamide, an aromatic polyamide (polyaramid), a polyamide-imide or mixtures thereof.
- Suitable second polyamides include, but are not limited to, nylon-6, nylon-11, nylon-12, nylon 6-6, nylon 6-10, nylon 6-11, nylon 6-12, nylon 6/66 copolymer, nylon 6/12/66 terpolymer, poly( para -phenylene terephthalamide), poly( meta -phenylene terephthalamide), poly( meta- xylene adipamide) (MXD6), and mixtures thereof.
- the polymer blend composition comprises a polymer blend comprising poly(trimethylene furandicarbonamide) (3AF) and a second furan-based polyamide different from 3AF, wherein the furan-based polyamide comprises the following repeat unit: wherein R is selected from the group consisting of an aliphatic, an aromatic and an alkylaromatic group.
- the polymer blend composition comprises a polymer blend comprising poly(trimethylene furandicarbonamide) (3AF) and poly(alkylene furandicarbonamide).
- Poly(alkylene furandicarboxylate) can be prepared from 2,5-furan dicarboxylic acid or a derivative thereof and a C 2 ⁇ C 18 aliphatic hydrocarbon or fluorocarbon diamine, as disclosed hereinabove.
- RAF poly(alkylene furandicarbonamide)
- R R1, R2 and R3.
- the polymer blend composition can further comprise additives commonly employed in the art such as process aids and property modifiers, such as, for example, antioxidants, plasticizers, UV light absorbers, antistatic agents, flame retardants, lubricants, colorants, nucleants, oxygen scavengers, fillers and heat stabilizers.
- additives commonly employed in the art such as, for example, antioxidants, plasticizers, UV light absorbers, antistatic agents, flame retardants, lubricants, colorants, nucleants, oxygen scavengers, fillers and heat stabilizers.
- polymer blend compositions comprising furan-based polyamides, as described above, are suitable for manufacturing the multilayer structures as defined in claim 1, which can themselves be used to make:
- a gas impermeable structure comprising two or more layers, wherein at least one of the layers is a gas permeation barrier layer comprising a furan-based polyamide comprises the following repeat unit: wherein R is selected from the group consisting of an aliphatic, an aromatic and an alkylaromatic group.
- R is a C2-C18 hydrocarbon or fluorocarbon group.
- the furan-based polyamide having structure (1) as shown above can be derived from furan dicarboxylic acid or derivative thereof and one or more diamines selected from the group consisting of an aliphatic diamine, an aromatic diamine and an akylaromatic diamine.
- Exemplary furan-based polyamide of structure (1) include, but are not limited to poly(trimethylene furandicarbonamide) (3AF), poly(ethylene furandicarbonamide) (2AF), poly(butylene furandicarbonamide) (4AF) poly(pentamethylene furandicarbonamide) (5AF), poly(hexamethylene furandicarbonamide) (6AF), poly(octyllene furandicarbonamide) (8AF), poly(trimethylene-co-hexamethylene furandicarbonamide), and mixtures thereof.
- the gas permeation barrier layer comprises poly(trimethylene furandicarbonamide) (3AF).
- the gas permeation barrier layer comprises a polymer blend composition, as disclosed supra , comprising a polymer blend of a furan-based polyamide and a polymer selected from the group consisting of polyurethanes, polyesters, polyolefins, polyamides, polyimides, polycarbonates, polyethers, polyacrylates, styrenics, fluoropolymers, polysiloxanes, EVOH and mixtures thereof.
- a polymer blend composition comprising a polymer blend of a furan-based polyamide and a polymer selected from the group consisting of polyurethanes, polyesters, polyolefins, polyamides, polyimides, polycarbonates, polyethers, polyacrylates, styrenics, fluoropolymers, polysiloxanes, EVOH and mixtures thereof.
- Figure 1 schematically illustrates a cross-sectional view of a portion of a multilayer structure 100 comprises at least two layers, in accordance with an embodiment of the present teachings.
- the multilayer structure 100 as shown in Figure 1 comprises a first layer 111 and a gas permeation barrier layer 110 disposed on at least a portion of the first layer 111, wherein the gas permeation barrier layer 110 provides a substantial barrier to gas permeation.
- the furan-based polyamide of the gas permeation barrier layer 110 is derived from:
- the furan-based polyamide comprises the following repeat unit: wherein R is selected from the group consisting of an aliphatic, an aromatic and an alkylaromatic group.
- R is a C2-C18 hydrocarbon or fluorocarbon group.
- the gas permeation barrier layer 110 comprises the polymer blend composition as disclosed hereinabove, comprising a polymer blend of the furan-based polyamide and a polymer selected from the group consisting of polyurethanes, polyesters, polyolefins, polyamides, polyimides, polycarbonates, polyethers, polyacrylates, styrenics, fluoropolymers, polysiloxanes, EVOH, and mixtures thereof, wherein the furan-based polyamide is present in an amount in the range of 0.1-99.9% by weight, based on the total weight of the polymer blend.
- the gas permeation barrier layer 110 comprises the polymer blend composition as disclosed hereinabove, comprising a polymer blend of the furan-based polyamide and a second polyamide selected from the group consisting of nylon-6, nylon-11, nylon-12, nylon 6-6, nylon 6-10, nylon 6-11, nylon 6-12, nylon 6/66 copolymer, nylon 6/12/66 terpolymer, poly( para-phenylene terephthalamide), poly( meta -phenylene terephthalamide), poly( meta -xylene adipamide) (MXD6), and mixtures thereof, wherein the furan-based polyamide is present in an amount in the range of 0.1-99.9% by weight, based on the total weight of the polymer blend.
- a second polyamide selected from the group consisting of nylon-6, nylon-11, nylon-12, nylon 6-6, nylon 6-10, nylon 6-11, nylon 6-12, nylon 6/66 copolymer, nylon 6/12/66 terpolymer, poly( para-phenylene terephthal
- the gas permeation barrier layer comprises a polymer blend comprising poly(trimethylene furandicarbonamide) (3AF) and a second furan-based polyamide different from 3AF, and wherein the amount of 3A is 0.1-99.9% by weight, based on the total weight of the polymer blend.
- the gas permeation barrier layer comprises a polymer blend comprising poly(trimethylene furandicarbonamide) (3AF) and a poly(alkylene furandicarbonamide), and wherein the amount of 3AF is 0.1-99.9% by weight, based on the total weight of the polymer blend.
- the gas permeation barrier layer 110 provides a substantial barrier to gas permeation.
- the gas permeation barrier layer 110 is moisture insensitive and provides a relatively constant gas permeability over a range of relative humidities.
- the first layer 111 is selected from the group consisting of polyurethane, polyester, polyolefin, polyamide, polyimide, polycarbonate, polyether, polyacrylates, styrenics, fluoropolymer, polyvinylchlorides, epoxies, EVOH and polysiloxanes.
- FIG. 2 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure 200 comprising at least three layers, in accordance with an embodiment of the present teachings.
- the multilayer structure 200 as shown in Figure 2 comprises a gas permeation barrier layer 210, a first layer 211, and a first tie layer 212 disposed between the gas permeation barrier layer 210 and the first layer 211, wherein the gas permeation barrier layer 210 comprises the furan-based polyamide compositions as disclosed hereinabove, and wherein the gas permeation barrier layer 210 provides a substantial barrier to gas permeation.
- FIG. 3 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure 300 comprising at least three layers, in accordance with an embodiment of the present teachings.
- the multilayer structure 300 as shown in Figure 3 comprises a gas permeation barrier layer 310 comprising the furan-based polyamide as disclosed hereinabove, a first layer 311 and a second layer 321, such that the gas permeation barrer layer 310 is sandwiched between the first layer 311 and the second layer 321, and wherein the gas permeation barrier layer 310 provides a substantial barrier to gas permeation.
- the multilayer structure 300 further comprises a first tie layer (not shown) disposed between the gas permeation barrier layer 310 and the first layer 311 and a second tie layer (not shown) disposed between the gas permeation barrier layer 310 and a second layer 321, such that the gas permeation barrier layer 310 is sandwiched between the first tie layer and the second tie layer.
- the multilayer structure of the present teachings may comprise other possible layer configurations not illustrated, including, but not limited to six layers, seven layers, eight layers, etc., wherein at least one layer is a gas permeation barrier layer comprising a furan-based polyamide, as disclosed herein above.
- the gas permeation barrier layer comprises a furan-based polyamide.
- the gas permeation barrier layer comprises the polymer blend composition comprising a blend composition of gas permeation barrier layer and another polymer, as disclosed hereinabove.
- the gas permeation barrier layer provides a substantial barrier to gas permeation in the multilayer structure.
- the gas permeation barrier layer is moisture insensitive and provides a relatively constant gas permeability over a range of relative humidities.
- the first layer 211, 311 and the second layer 321 may be any suitable material, including, but not limited to polymers, composites, metals, alloys, glass, silicon, ceramics, wood, and paper.
- the first layer is selected from the group consisting polyurethane, polyester, polyolefin, polyamide, polyimide, polycarbonate, polyether, polyacrylates, styrenics, fluoropolymer, polyvinylchlorides, epoxies, EVOH and polysiloxanes.
- Exemplary materials for the first layer 211, 311, 411 and the second layer 421 include, but are not limited to aramids; polyethylene sulfide (PES); polyphenylene sulfide (PPS); polyimide (PI); polyamide (PA) such as Nylon; polyethylene imine (PEI); polyethylene naphthalate (PEN); polysulfone (PS); polyether ether ketone (PEEK); polyolefins such as PE, HDPE, LDPE, LLDPE, ULDPE, PP; poly(cyclic olefins); and poly(cyclohexylene dimethylene terephthalate), EvOH, poly(alkylene furandicarboxylate) such as PEF, PTF, PBF and poly(alkylene terephthalate), such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT).
- PES polyethylene sul
- the first layer 211, 311 and the second layer 321 comprises an aliphatic polyamide, an aromatic polyamide (polyaramid), a polyamide-imide or mixtures thereof.
- Suitable polyamides for the first layer and the second layer include, but are not limited to nylon-6, nylon-11, nylon-12, nylon 6-6, nylon 6-10, nylon 6-11, nylon 6-12, nylon 6/66 copolymer, nylon 6/12/66 terpolymer, poly( para -phenylene terephthalamide), poly( meta -phenylene terephthalamide), poly( meta- xylene adipamide) (MXD6), and mixtures thereof.
- the tie layer 212 as shown in Figure 2 comprises one or more olefin copolymers.
- the one or more olefin copolymers include, but are not limited to, propylene copolymers, ethylene copolymers and mixtures thereof.
- Propylene copolymer refers to a polymer comprising repeat units derived from propylene and at least one additional monomer.
- Suitable propylene based copolymers include, but are not limited to, copolymers of propylene with another ⁇ -olefin as a monomer, including but not limited to ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene or 4-methyl-1-pentene.
- Other comonomers include but not limited to maleic anhydride, acrylic acid, acrylates and methacrylates. Copolymers could be either random or block copolymers.
- Ethylene copolymer refers to a polymer comprising repeat units derived from ethylene and at least one additional monomer.
- the one or more ethylene copolymers comprised in the tie layer of the multilayer structure may be chosen among ethylene ⁇ -olefin, ethylene vinyl acetate copolymers, ethylene maleic anhydride copolymers, ethylene acrylic acid (or the neutralized salt form of the acid) copolymers, ethylene methacrylic acid (or the neutralized salt form of the acid) copolymers, ethylene glycidyl (meth)acrylate copolymers, ethylene alkyl (meth)acrylate copolymers, or combinations of two or more thereof.
- Alkyl (meth)acrylate refers to alkyl acrylate and/or alkyl methacrylate.
- Ethylene alkyl (meth)acrylate copolymers are thermoplastic ethylene copolymers derived from the copolymerization of ethylene comonomer and at least one alkyl (meth)acrylate comonomer, wherein the alkyl group contains from one to ten carbon atoms and preferably from one to four carbon atoms. More preferably, the ethylene copolymer comprised in the tie layer are chosen among ethylene ⁇ -olefin, ethylene vinyl acetate copolymers, ethylene methyl (meth)acrylate copolymers, ethylene ethyl (meth)acrylate copolymers, ethylene butyl (meth)acrylate copolymers, or combinations of two or more thereof.
- the ethylene copolymer used in the tie layer is an ethylene ⁇ -olefin copolymer, it comprises ethylene and an ⁇ -olefin of three to twenty carbon atoms.
- Preferred ⁇ -olefin include four to eight carbon atoms.
- the one or more olefin homopolymers and/or copolymers can be modified copolymer, meaning that the copolymer is grafted and/or copolymerized with organic functionalities.
- Modified polymers for use in the tie layer may be modified with acid, anhydride and/or epoxide functionalities.
- acids and anhydrides used to modify polymers which may be mono-, di- or polycarboxylic acids are acrylic acid, methacrylic acid, maleic acid, maleic acid monoethylester, fumaric acid, furnaric acid, itaconic acid, crotonic acid, 2,6-naphthalene dicarboxylic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydride, e.g. dimethyl maleic anhydride or citrotonic anhydride, nadic anhydride, nadic methyl anhydride, and tetrahydrophthalic anhydride, or combinations of two or more thereof, maleic anhydride being preferred.
- epoxides used to modify polymers are unsaturated epoxides comprising from four to eleven carbon atoms, such as glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether and glycidyl itaconate, glycidyl (meth)acrylates being particularly preferred.
- Epoxide-modified ethylene copolymers preferably contain from 0.05 to 15 wt% of an epoxide, the weight percentage being based on the total weight of the modified ethylene copolymer.
- epoxides used to modify ethylene copolymers are glycidyl (meth)acrylates.
- the ethylene/glycidyl (meth)acrylate copolymer may further contain copolymerized units of an alkyl (meth)acrylate having from one to six carbon atoms and an .alpha.-olefin having 1-8 carbon atoms.
- Representative alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, or combinations of two or more thereof.
- ethyl acrylate and butyl acrylate are ethyl acrylate and butyl acrylate.
- the ⁇ -olefin can be selected from the group of propylene, octene, butene and hexane, especially propylene.
- modified ethylene copolymers comprised in the tie layer are modified with acid, anhydride and/or glycidyl (meth)acrylate functionalities.
- Exemplary ethylene based copolymers include, but are not limited to, polyethylene-co vinylacetate, polyethylene-co-methylacrylate, polyethylene-co-maleic anhydride, polyethylene-co-acrylate (i.e. methylacrylate, ethylacrylate, butylacrylate etc), polyethylene-co-glycidylacrylate, polyethylene-co-glycidylmethacrylate, polyethylene-covinylalcohol, polyethylene-co-acrylic acid; polyethylene-co-acrylic acid sodium salt, polyethylene-co-methylmethacrylate, polyethylene-co-methacrylic acid, and polyethylene-co-methacrylic acid sodium salt.
- Copolymers and modified polymers useful for the present teachings are commercially available for example under the trademarks Nucrel®, Surlyn®, Elvax®, ElvaloyTMAC, ElvaloyTM, Bynel® from E. I. du Pont de Nemours and Company, Wilmington, Del. (DuPont).
- tie layers could also be used to improve the adhesion between layers comprising polar materials, for example polyamides and polyesters.
- examples of such tie layers include but are not limited to, polyacrylates, aromatic polyesters, aliphatic polyesters, aliphatic-aromatic copolyesters, polyamides, polyesteramides, polyvinyl alcohol, aliphatic polycarbonates, aromatic polycarbonates, polymaleic anhydride or grafted polymaleic anhydride, polyvinylacetate, polyvinylacetate-co-maleic anhydride, polyvinylalcohol-co-vinylacetate, polyacrylate-co-vinylacatete, polyacrylate-covinylalcohol, polyacrylate-co-maleic anhydride, polyvinylalcohol-co-maleic anhydride, polyacrylic acid or the neutralized salt form of the acid, polyacrylic acid-co-vinyl alcohol, polyacrylic acid-co-vinyl acetate, polyacrylic acid-co-maleic anhydr
- the gas permeation barrier layer 110, 210, 310 has a thickness in the range of 0.1-80% or 0.5-50% or 1-25% of the total thickness of the multilayer structure to provide a permeation barrier to a gas.
- the multilayer structure is a co-extruded multilayered structure. In another embodiment, the multilayer structure is a laminated structure.
- an article comprising the multilayer structure 100, 200, 300.
- the article can be a film, a sheet, a coating, shaped or modeled article, a layer in a multi-layer laminate, for example a shrink-wrap film., filaments, fibers, spun yarn, woven fabric, garment, or non-woven web.
- a film herein can be oriented or not oriented, or uniaxially oriented or biaxially oriented.
- a sheet will be defined herein as having a thickness greater than about 0.25 mm (10 mils).
- the thickness of the sheets herein are from about 0.25 mm to about 25 mm, more preferably from about 2 mm to about 15 mm, and even more preferably from about 3 mm to about 10 mm.
- the sheets hereof have a thickness sufficient to cause the sheet to be rigid, which generally occurs at about 0.50 mm and greater.
- sheets thicker than 25 mm, and thinner than 0.25 mm may be formed.
- films as formed from the polymers hereof will in almost all cases have a thickness that is less than about 0.25 mm.
- a film herein can be single layer or multilayer; oriented or not oriented; or uniaxially oriented or biaxially oriented.
- a film comprising a furan-based polyamide, as disclosed hereinabove, in the form of a homopolyamide, a copolyamide or a blend of furan-based polyamide with another polyamide exhibits moisture insensitivity, demonstrated by relatively constant gas permeability with change in relative humidity, as compared to other moisture sensitive polymers, such EVOH and Nylon.
- a film comprising a furan-based polyamides, as disclosed hereinabove, can be characterized by an oxygen permeability of less than about 100 cc-mil/m 2 -day-atm or less than 50 cc-mil/m 2 -day-atm or less than 30 cc-mil/m 2- day-atm or less than 20 cc-mil/m 2 -day-atm less than 10 cc-mil/m 2 -day-atm less than 1 cc-mil/m 2 -day-atm; or a carbon dioxide permeability of less than about 500 cc-mil/m 2 -day-atm or less than 250 cc-mil/m 2 -day-atm or less than 100 cc-mil/m 2 -day-atm or less than 50 cc-mil/m 2 -day-atm or less than 25 cc-mil/m 2 -day-atm or less than 5 cc
- Fiber is defined as a relatively flexible, unit of matter having a high ratio of length to width across its cross-sectional area perpendicular to its length.
- fiber is used interchangeably with the term “filament” or “end” or “continuous filament”.
- the cross section of the filaments described herein can be any shape, such as circular or bean shaped, but is typically generally round, and is typically substantially solid and not hollow. Fiber spun onto a bobbin in a package is referred to as continuous fiber. Fiber can be cut into short lengths called staple fiber. Fiber can be cut into even smaller lengths called floc.
- Yarns, multifilament yarns or tows comprise a plurality of fibers. Yarn can be intertwined and/or twisted.
- the article can be a shaped or molded article, such as one or more of a container, a container and a lid, or a container and a closure, for example a container such as a beverage container.
- the multilayer structure as disclosed herein above is in a form of a housing provided with a port for introducing a product in an enclosure defined by the housing, wherein the multilayer structure provides gas permeation barrier to the product.
- the product is an oxygen-sensitive product.
- oxygen-sensitive product includes, but is not limited to, microbial culture, foods, chemicals.
- the product is a moisture-sensitive product.
- Exemplary moisture-sensitive product includes, but is not limited to, food products, hygroscopic polymers like EVOH or ionomers.
- the product is a carbonated beverage.
- the product is a hydrocarbon fuel.
- the housing is in a form of a hose, a pipe, a duct, a tube, a tubing or a conduit.
- the housing is in a form of a container, a container and a lid, or a container and a closure.
- the multilayer structure is in a form of a hollow body selected from a group consisting of a hose, a pipe, a duct, a tube, a tubing or a conduit.
- the product is a chemical solvent based product and the multilayer structure is in a form of a bottle.
- Suitable chemical solvents include, but are not limited to, ethanol, methanol, ketones, toluene, xylene, isooctane, gasoline, kerosene, and mineral spirits.
- Examples of chemical solvent based products include, but are not limited to, household and industrial solvents, agricultural chemical products.
- the gas includes, but is not limited to, oxygen, carbon dioxide, water vapor, nitrogen, methane, chlorine, hydrogen sulfide, refrigerants, and vapors of chemical solvents.
- the gas comprises oxygen, carbon dioxide and water vapor.
- an article for storage or transport of a product comprising the multilayer structure as disclosed hereinabove, in a form of a housing provided with a port for introducing said product in an enclosure defined by the housing, wherein the multilayer structure provides permeation barrier to the product.
- the product is at least one of an oxygen sensitive product or a moisture sensitive product.
- the article may further comprise means for closing the port, such that upon closing the port, the product is isolated from the outside environment.
- the article may comprise one or more of a container, a container and a lid, or a container and a closure.
- the article as disclosed herein above comprising a furan-based polyamide can be used for any suitable application, including, but not limited to food and drug packaging, medical devices, personal care products, electronics and semiconductors, paints and coatings, and chemical packaging.
- barrier layer 110, 210, 110; the first or the second layer 311; and the tie layer 212 described hereinabove may contain one or more additives including, but not limited to, antioxidants, plasticizers, UV light absorbers, antistatic agents, flame retardants, lubricants, colorants, nucleants, oxygen scavengers, fillers and heat stabilizers.
- Suitable antioxidants include, but are not limited to, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 4,4'-thiobis-(6-tertbutylphenol), 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis-(6-tertbutylphenol), etc.
- Suitable UV light absorbers include, but are not limited to, ethylene-2-cyano-3,3'-diphenyl acrylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.
- Suitable plasticizers include, but are not limited to, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, waxes, liquid paraffins, phosphoric acid esters, etc.
- Suitable antistatic agents include, but are not limited to, pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbon wax, etc.
- Suitable lubricants include, but are not limited to, ethylene bisstearoamide, butyl stearate, etc.
- Suitable colorants include, but are not limited to, carbon black, phthalocyanine, quinacridon, indoline, azo pigments, red oxide, etc.
- Suitable filler include, but are not limited to, glass fiber, asbestos, ballastonite, calcium silicate, talc, montmorillonite, etc.
- Suitable nucleants to induce crystallization in the furan-based polyamide include, but are not limited to fine dispersed minerals like talc or modified clays.
- Suitable oxygen scavengers to improve the oxygen barrier include, but are not limited to, ferrous and non-ferrous salts and added catalysts.
- a method of making a gas-impermeable product comprising forming a multilayer structure having two or more layers, wherein at least one of the layers is a gas permeation barrier layer comprising a furan-based polyamide, as disclosed hereinabove.
- a size exclusion chromatography system Alliance 2695TM (Waters Corporation, Milford, MA), was provided with a Waters 414TM differential refractive index detector, a multi-angle light scattering photometer DAWN Heleos II (Wyatt Technologies, Santa Barbara, CA), and a ViscoStarTM differential capillary viscometer detector (Wyatt).
- the software for data acquisition and reduction was Astra® version 5.4 by Wyatt.
- the columns used were two Shodex GPC HFIP-806MTM styrene-divinyl benzene columns with an exclusion limit of 2 x 107 and 8,000/30cm theoretical plates; and one Shodex GPC HFIP-804MTM styrene-divinyl benzene column with an exclusion limit 2 x 10 5 and 10,000/30cm theoretical plates.
- the specimen was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) containing 0.01 M sodium trifluoroacetate by mixing at 50 °C with moderate agitation for four hours followed by filtration through a 0.45 ⁇ m PTFE filter. Concentration of the solution was circa 2 mg/mL.
- HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
- Intrinsic viscosity was determined using the Goodyear R-103B Equivalent IV method, using T-3, Selar® X250, Sorona®64 as calibration standards on a Viscotek® Forced Flow Viscometer Modey Y-501C. Methylene chloride/trifluoro acetic acid was used as a solvent carrier for Example 1, whereas Phenol/1,1,2,2-tetrachloroethane (60/40) was used for Examples 4-10.
- T g Glass transition temperature
- T m melting point
- Example 1 2,5-furandicarboxylic acid (FDCA) was obtained from Sarchem labs (Farmingdale, NJ), whereas for Examples 4-10, 2,5 furan dicarboxylic acid (99+% purity) was obtained from AstaTech Inc. (Bristol, PA). Chloroform (Drisolv®) was obtained from EDM and used as received. PET (Polyclear PET 1101) was obtained from Indorama Corporation. MXD6 (Polyamide MXD6/Nylon-MXD6) from MGC Advanced Polymers (S Chesterfield, VA). All chemicals were used as received unless otherwise specified.
- Example 1 Preparation of a Furan-Based Polyamide (poly(trimethylene furandicarbonamide) (3AF)) Film And Measurement of 3AF Film Barrier Properties
- Step 1A Preparation of 2,5-furandiacid chloride (FDC-Cl)
- Step 1B Preparation of Furan-Based Polyamide (poly(trimethylene furandicarbonamide) (3AF)) from FDC-Cl and 1,3-diaminopropane
- the steel bar was rotated at a speed of 100 rpm and the polyamide film was captured with continuous stirring for about 120 minutes. After completion of the polymerization the polymer was removed from the stir bar, washed continuously with distilled water and acetone. The washed polymer was placed in a vacuum oven and dried under vacuum at 70 °C until a constant weight was reached. ⁇ 7g of the furan-based polyamide, poly(trimethylene furandicarbonamide) (3AF) was collected after drying for 24 hours. T g was ca. 171°C (DSC, 10°C/min, 2 nd heat), no melting was observed. TGA confirmed thermal stability up to 400°C.
- Step 1C Preparation of a Film from the Furan-Based Polyamide, 3AF obtained in Step 1B
- the 3AF polymer prepared above was compression molded into 0.1-0.12 millimeter thick films using a hydraulic platen press.
- the polymer was placed in a 15x15 centimeter frame supported on Kapton® film.
- the polymer sample and the Kapton® film was placed between two sheets of fiberglass reinforced Teflon® and in turn between two brass sheets and placed into a pre-heated Pasadena press.
- the press was pre-heated to a temperature of 220°C and the film sandwich was placed between the platen.
- the film sandwich was treated at 0 psig for 6 minutes to achieve a uniform melt before applying pressure.
- the pressure was raised to 10,000 psig and held for 8 minutes.
- the sample was removed from the press and put into an ice bath to rapidly quench the film.
- the produced and quenched film was separated from the Teflon® sheet, and measured for its permeation. DSC confirmed that films so produced were fully amorphous and no melting was observed.
- Step 1D Gas Barrier Performance of the Furan-Based Polyamide, 3AF
- Example 1 A procedure similar to step 1D of Example 1 was used to analyze PET (Laser 9921) polymer films for their permeation towards oxygen and carbon dioxide. Results are summarized in Table 1.
- Table 1 Gas Permeability (50%RH, 23°C) Sample Morphology Oxygen Permeability (cc-mil/m 2 - day) Carbon Dioxide permeability (cc-mil/m 2 - day)
- Example 1 3AF amorphous 2.5 70 Comparative Example A PET amorphous 164 ⁇ 1000
- the furan-based polyamide, 3AF poly(trimethylene furandicarbonamide)
- PET poly(ethylene terephthalate)
- Example 1 Comparative Example B Comparative Example C Polymer 3AF MXD6 EvOH Oxygen Permeability (cc-mil/m2-day) at Relative Humidity (RH) 0% RH 0.7 13.1 0.3 35% RH - 5.7 - 50% RH 2.5 4.9 - 63% RH - - 1.2 75% RH - 5.7 - 80% RH 2.3 - - 85% RH - - 14 87% RH - 5.3 - 100% RH - - 33.5
- the furan-based polyamide, 3AF poly(trimethylene furandicarbonamide)
- MXD6 moisture-insensitive polyamide
- Example 2 Preparation of Film from a Composition comprising a blend of 3AF and Nylon-6
- Example 3 Preparation of a Multilayer Structure, Nylon-6/3AF/Nylon-6 Laminate film
- Step 3A Preparation of Laminate precursor 1, Nylon-6 film
- Nylon-6 film was prepared by Nylon-6 pellets. Pellets were dried for a minimum of 12 hours in a vacuum oven at 80°C, under vacuum with nitrogen flow. After drying, a Pasadena PHI P-215C heated press was set to ⁇ 10 °C above the melting point of the polymers to be pressed. Once the desired temperature was achieved, ⁇ 1g of dried sample pellets were placed between two pieces of gold Teflon® paper and placed in the open press. The upper press platen was then lowered until contact was made with the top of the samples. After ⁇ 7 minute of temperature equilibration, pressure was slowly increased on the sample to 5,000 LB ( ⁇ 78PSI) for 2 min then increased to 10,000 LB ( ⁇ 156 PSI) for 5 min. Then the sample was quickly removed from the oven and quenched in an ice water bath. The resulted film was 8 mil thick haze film, which was cut in half to be used in making a laminate with 3AF.
- Step 3B Preparation of Laminate precursor 2: 3AF film
- Step 3C Preparation of Multilayer Structure, Nylon-6/3AF/Nylon-6 Laminate film
- the laminates were composed with one layer of above Nylon-6 film at the bottom and 3AF film in the middle, and the same Nylon-6 film on top.
- the final laminate film was prepared by hot pressing at 260 °C for 2 min.
- the resulted film was ⁇ 12 mil thick haze film.
- the resulted laminate of Nylon-6 and 3AF was tested for the oxygen barrier test. Summarized in Table 3 are permeation results for oxygen.
- Example 3 A procedure similar to step 3C of Example 3 was used to analyze Nylon-6 polymer film for permeation towards oxygen. Results are summarized in Table 3.
- Table 3 Gas Permeability (50%RH; 23°C) Sample Composition: 3AF/Nylon-6 by weight% Oxygen Permeability (cc-mil/m 2 -day)
- Example 3 Nylon-6/3AF/Nylon-6 ⁇ 28/72 16 Comparative
- Example D Nylon-6 0/100 ⁇ 35 Comparative Example A PET -- 164
- Example 4 Preparation of furan-based polyamide from FDC-Cl,TPA-Cl, and 1,3-diaminopropane (PDA) using Interfacial Polymerization.
- Step 4A Preparation of Furan Diacid Chloride (FDC-Cl):
- FDC-Cl was prepared in a smaller batch with the materials and procedure outlined in Step 1A using a 250 mL round bottom flask.
- 13C-NMR (CH2Cl2-d) ⁇ : 124.04 (-CH), 149.71 (-C-), 156.36 (C O).
- Step 4B Preparation of Furan-Based Polyamide from FDC-Cl,TPA-Cl, and 1,3-diaminopropane (PDA)
- a furan-based polyamide was synthesized from the monomers: FDC-Cl, TPA-Cl and 1,3-diaminopropane (PDA), the feed amounts of which are summarized in Table 4.
- an aqueous solution was prepared in a 1 L-beaker by charging it with 6.7 g of sodium hydroxide, 7.3 g of propanediamine (PDA), and 800 mL distilled water, and stirring using a magnetic stir bar until dissolution occurred.
- the aqueous solution was slowly charged to the beaker containing the organic solution to creating a two layer system whereby the organic phase was the bottom layer.
- a polymer product was generated at the interface between the aqueous layer and the organic layer which was pulled up using a pair of tweezers and attached to the automatically rotating bar.
- the polymer product was continuously drawn from the interface and twisted around the automatically rotating bar.
- the reaction was performed for about 1-3 hours while the speed was kept constant to thereby obtain a polymer product.
- the generated polymer product was washed with water and dried under vacuum at 110 °C for 1 day.
- the weight average molecular weight of the as-prepared furan-based was 65000 g/mole, as determined by Gel Permeation chromatography (GPC).
- the intrinsic viscosity of the as-prepared furan-based polyamide was determined to be 0.763 dL/g, by solution viscometry.
- T g was ca. 169 °C (DSC, 10°C/min, 2nd heat).
- Mole % values, in the final polymer as provided in 6 were calculated by integration from the 1 H NMR spectra.
- 1 H-NMR (CF 3 COOH-d) ⁇ : 8.09 (m, 4H), 7.49 (m, 2H), 3.89 (m, 4H), 2.26 (m, 2H).
- Table 4 Summary of molar feed ratios Example # Mole % TPA Mole % FDCA Mole % PDA Mole % HMD Example 4 50 50 100 0 Example 5 25 75 100 0 Example 6 25 75 0 100 Example 7 0 100 50 50 Example 8 25 75 50 50 Example 9 (3AF) 0 100 100 0 Example 10 (6AF) 0 100 0 100
- Step 4C Preparation of Melt-Pressed Films:
- Example 1C dry solids of the polymers were pressed between two PTFE-coated sheets at 220 °C at 10,000 lb of force for 2 minutes on a Pasadena hot press to make the film (3-10 mil). The film was cooled in air at a rate 200-400 °C/min.
- a furan-based polyamide was synthesized from FDC-Cl, TPA-Cl and 1,3-diaminopropane (PDA) using procedure described in Example 4, except that the monomer feed amounts of FDC-Cl and TPA-Cl were changed, as given in Table 4.
- the weight average molecular weight of the polymer as determined by Gel Permeation chromatography (GPC), the intrinsic viscosity as determined by solution viscometry, and the T g (DSC, 10°C/min, 2nd heat) are provided in Table 5.
- Mole % values, in the final polymer as provided in Table 5 were calculated by integration from the 1 H NMR spectra.
- 1 H-NMR (CF 3 COOH-d) ⁇ : 8.09 (m, 4H), 7.49 (m, 2H), 3.89 (m, 4H), 2.26 (m, 2H).
- a furan-based polyamide was synthesized from FDC-Cl, TPA-Cl and hexamethylene diamine (HMD) using procedure described in Example 4, except that HMD was used instead of PDA and the amounts of FDC-Cl and TPA-Cl were changed as shown in Table 4.
- the weight average molecular weight of the polymer as determined by Gel Permeation chromatography (GPC), the intrinsic viscosity as determined by solution viscometry, and the T g (DSC, 10°C/min, 2nd heat) are provided in Table 5.
- a furan-based polyamide was synthesized from FDC-Cl, diaminopropane (PDA) and hexamethylene diamine (HMD) using procedure described in Example 4, except that only FDC-Cl was used instead of both FDC-Cl and TPA-Cl, and that two diamines were used HMD and PDA as shown in Table 4.
- the weight average molecular weight of the polymer as determined by Gel Permeation chromatography (GPC), the intrinsic viscosity as determined by solution viscometry, and the T g (DSC, 10°C/min, 2nd heat) are provided in Table 5.
- Mole % values, in the final polymer as provided in Table 5 were calculated by integration from the 1 H NMR spectra.
- 1 H-NMR (CF 3 COOH-d) ⁇ : 7.57-7.49 (m, 2H), 3.9-3.6 (m, 8H), 2.24 (m, 2H), 1.87 (m, 4H), 1.62 (m, 4H).
- Example 8 Preparation of Furan-Based Polyamide from FDC-Cl, TPA-Cl, 1,3-diaminopropane (PDA) and hexamethylene diamine (HMD)
- a furan-based polyamide was synthesized from FDC-Cl, TPA-Cl, PDA and hexamethylene diamine (HMD) using procedure described in Example 4, except the monomer feed amounts of FDC-Cl and TPA-Cl were changed, and two diamines were employed, as shown in Table 4.
- the weight average molecular weight of the polymer as determined by Gel Permeation chromatography (GPC), the intrinsic viscosity as determined by solution viscometry, and the T g (DSC, 10°C/min, 2nd heat) are provided in Table 5.
- Mole % values, in the final polymer as provided in Table 5 were calculated by integration from the 1 H NMR spectra.
- Example 4 In preparing a separate batch of 3AF, the same material demonstrated in Example 4, a 500ml three-necked flask equipped with a nitrogen adaptor, mechanical stirrer, glass stir rod with a Teflon blade, and a drop funnel was set up. To the flask was charged 7.352 g (0.0248 mol) 1,3-propanediamine (PDA) in 160ml of water containing 7.12 g of NaOH. In dry box, a solution of 21.032g (0.109 mol) of 2,5-furan dicarboxylic acid chloride (FDC-Cl) in 160ml of dry chloroform was prepared. The chloroform solution was transferred into the drop funnel connected to the flask.
- PDA 1,3-propanediamine
- the aqueous solution in the flask was stirred under nitrogen at ⁇ 500rpm in an ice water bath.
- the chloroform solution was added to the 500 mL flask through the drop funnel as a steady slow stream, immediately forming white solids.
- the mixture was stirred for 1 hour at 500 rpm and then at 200 rpm overnight. After stirring was stopped, the white solids were washed with water 3-5 times and then isolated by decanting.
- the obtained crude polymer was chopped into small pieces and placed in a 500 mL round bottom flask equipped with a magnetic stir bar and a condenser. Methanol (400 mL) was added and the mixture was heated at 60 °C for 48 hours, during which the methanol was refreshed after 24 hours. After cooling, the polymer was isolated, washed by water and then acetone, and dried in a vacuum oven at 40 °C. The final product was a white solid with 55% yield.
- a furan-based polyamide was synthesized from FDC-Cl and HMD using the procedure described in Example 9. The final product was a white solid with 39% yield.
- Table 5 Summary of properties of the resulting furan-based polyamides and polyamides Example # Mole % TPA Mole % FDCA Mole % PDA Mole % HMD Mw (Kg/mol) IV (dL/g) Tg (°C) Example 4 37 63 100 0 65 0.763 169 Example 5 19 81 100 0 47 0.449 162 Example 6 24 76 0 100 107 0.735 142 Example 7 0 100 35 63 108 1.082 154 Example 8 18 82 37 62 114 0.997 145 Example 9 0 100 100 0 82 0.90 170 Example 10 0 100 0 100 166 1.62 143
- Examples 4-8 demonstrate that furan-based polyamides can be formed starting from three monomers or four monomers in any combination such as two diacids and a diamine as in Examples 4-6, or one diacid and two diamines as in Example 7, or two diacids and two diamines as in Example 8 using an interfacial copolymerization. Furthermore, the resulting composition of the polyamide can be tuned by changing the monomer feedstock through using different amounts of the diacids and diamines.
- Such polyamides are likely to demonstrate beneficial performance in structures comprising monolayers, coatings, laminates, multilayers, and/or blends where differentiated material properties are desired compared to FDCA-based polyamide homopolymers and/or other polyamides.
- the polyamides of Examples 4-8 can be used as to prepare monolayer films, using procedure similar to Example 1C.
- monolayer or multilayer structures can be formed using compositions comprising blends of furan-based polyamides with other polyamides, such as nylon or other furan-based polyamides, such as Example 1, 9-10, using procedure as outlined in Example 2 and 3 respectively.
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US20160009015A1 (en) * | 2012-08-31 | 2016-01-14 | Societe Anonyme Des Eaux Minerales D'evian S.A.E.M.E | Bottle, method of making the same and use of fdca and diol monomers in such bottle |
US20190001262A1 (en) * | 2015-07-24 | 2019-01-03 | E I Du Pont De Nemours And Company | Gas separation membrane using furan-based polymers |
WO2018065515A1 (en) * | 2016-10-05 | 2018-04-12 | Plastic Omnium Advanced Innovation And Research | Composite pressure vessel with a monolayer liner |
MX2019013127A (es) * | 2017-05-11 | 2020-07-22 | Dupont Polymers Inc | Artículos híbridos de metal y polímero. |
EP3418316A1 (de) | 2017-06-19 | 2018-12-26 | Basf Se | Polymerfilme mit erhöhter sauerstoffbarriere |
WO2019020065A1 (zh) * | 2017-07-28 | 2019-01-31 | 东丽先端材料研究开发(中国)有限公司 | 一种热塑性树脂组合物与金属的接合体及其制造方法 |
CN110256668B (zh) * | 2019-06-04 | 2021-12-10 | 中国科学技术大学 | 高分子量呋喃基芳香聚酰胺及其制备方法和应用 |
CN111961199B (zh) * | 2020-09-02 | 2022-01-28 | 中国科学院宁波材料技术与工程研究所 | 生物基耐高温聚酰胺复合材料、其制备方法及应用 |
CN113199842B (zh) * | 2021-04-29 | 2022-08-16 | 厦门长塑实业有限公司 | 一种低光泽高透明的聚酰胺薄膜及其制备方法 |
CN113896886B (zh) | 2021-09-24 | 2023-07-25 | 珠海万通特种工程塑料有限公司 | 一种呋喃二酸基聚酰胺及其制备方法和一种呋喃二酸基聚酰胺组合物 |
CN113817159B (zh) * | 2021-09-24 | 2023-10-13 | 珠海万通特种工程塑料有限公司 | 一种呋喃二酸基聚酰胺树脂及其制备方法和一种聚酰胺模塑组合物 |
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US20100029821A1 (en) * | 2008-07-30 | 2010-02-04 | E. I. Du Pont De Nemours And Company | Heat resistant thermoplastic articles including co-stabilizers |
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WO2014012240A1 (en) * | 2012-07-20 | 2014-01-23 | Rhodia Operations | Novel polyamide, preparation process therefor and uses thereof |
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US9938376B2 (en) * | 2013-10-21 | 2018-04-10 | Synvina C.V. | Process for preparing a furan-based polyamide, a furan-based oligomer and compositions and articles comprising the furan-based polyamide |
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